Methanol Thermodynamic Properties From 176 to 673 K at Pressures to 700 Bar Robert D. Goodwin Thormophyee ivson, National Engineering Laboratory, National Bureau of Standards, oulder,Coloede 80203 ‘Receive Jnusry 30, 1987; revised manuscript eve Jane 11987 Available data for vapor pressures and for the orthobaric densities of methanol are ‘examined and formulated. Then, PpT data are correlated by an equation of state (EOS) Which is constrained tothe given coexistence boundary. Via ideal gas state specific heats, the thermodynamic properties of methanol then are obtained by numerical integrations of the EOS, and are tabulated along isobars. A comparison is made with some recent calori- metre enthalpy diferensoe date over # wide range of Key words: compressibility factors; densities; enthalpies; entropies; equation of state; fugaciies, ‘nats of vaporization; ideal gas, JouleThomsoncoeficiens; methanol orthobarc densities; speci ‘nets speeds or sound; hermodynamic properties; vapor pressures; vr coemcients, Contents 1. Introduction nn 800 6. Acknowledgments. 2. Developing the Equation of State. 8017. Refer 2088 nn 24. Methanol Vapor Pressures 801 22, Methanol Orthobarie Densities 301 2.2. Saturated Liquid Densities 801 List of Tables 2.20, Saturated Vapor Densities... 805 1, Selected fixed-point values for methanal 22e: Alienate Vapor Densities Ems 2, Summary of vapor-preaure data fr methanol tion 810 3, Methanol vapor-pressure daa. 23. The Virial Equation. 810 4, Summary of orthobaricdensities data for 24, Pressure-Density—Temperature Data 811” ethanol 23. The Equation of Site ncn S11 5, Methanol saturated liquid densities data 3. Thermal Properties and Computations.vwnmnn 844 6 Methanol saturated vapor densities data 3.1. Funetions for Ideal Gas States 844 7, Summary of PpT data for methane! 29) The Homngenanne Pom 844g, Zuuer wrtdmuliattesen dung 3.3. Properties at Coexsten0? cso 846 9. Comparison of foT daa for methandl 3.3.8. Specific Heats on the Vapor Bound- 10. Methanol critical isotherm... ay 6 fethanol ideal as state data... 5-80, Sturt Ligua tains andi: 2, Methanol nerpoled eal gu sas actos tropics 848 13, Comparison with methanol , (7) data of Carl 3.3. Saturated Liquid Specific Heats... 848 son/Westrum, 1971 24 Compreneed Liquid Statee Ht 14, Conpatwm of maton coaayy Gea, 3.5. Comparisons sr : 848 15, Joule~Thomson inversion locus for methanol 4 Tables of Thermophysial Properties. 849 16. Properties of saturated liquid methanol 41 The Joule-Thomson Inversion Locus 849 17, Properties of methanol along isobars.. 42. Properties at Coexistence enna 349 43. Properties Along Sltdobars 849 5. Comments... é 349 01987 bythe US. Serer of Commerc ce behalf the United State: “his copyright i sled to the American Ist of Phys and the Reponts vale rom ACS se Reprints Lis at bck of issue (0047-2609/67/040708-94/810.00 List of Figures 1. Methanol coexistence boundary 2, Methanol vapor densities deviations... 3. Derived C, (7). atthe liquid boundary... 4. Comparison of enthalpy differences at 515.2 K. B91 891 201 801 802 808 805 807 sit 815 845 846 847 848 851 852 810 849 351 «1. Phys. Chem. Ret. Data, Vol. 16, No.4, 1967‘Symbols and Units Subscnpts¢ and t refer to critical and liquid triple points Subscripts g and I refer to saturated vapor and liquid Suberipto refers to liquid-vapor coexistence (9.740, exponents in vartous functions B(),C(T) virial coeficients, Eq. (4) saturated liguid specific heat, Jmol~! K~! inochorie specific heat3 mal" K~' isochoric specific heat at the critical point (CP), 161.143 mol“! K* isochorie specific heat a th liquid boundary, Imot*K* isobaric specific heat, Jmol~! K-* internal energy, 1/mol 3 374.762 ¥/mol (arbitrary) fugacity, bar fugacity/pressure coeficient defined function in the EOS ‘00s energy, 3/mo! enthalpy, J/mol for ideal gas state at 32,0424 g of methanol (molecular weight) pressure, bar (1 bars 10° N/m*) 4.013 25 bar (1 atm) vapor pressure of saturated liquid, bar PIT, (p)], vapor pressure as function of density, bar Qn AML, heat oF vaporization, T/mal R ‘gas constant, 8.3145 J mol K, 0,083 145 (ar L/mol) /K eo density, mol/L. ° ip, Feduced density % (0.825, reversal of isochore curvatures, Eq. © * ul enced Vail Aonity ot teple paint 30 1d DENSITY, mol/L 4 Phva. Chem. Re. Dats. Val. 16. No 4.1987 ROBERT D. aooDWIN S@.T) entropy, Jmol! K-* r temperature, K T,(p) __liquid-vapor coexistence temperature u(T) defined where used x(7) defined where used > ‘Vp, molal volume, L/mol W(p.T) speed of sound, m/s Z(P,pkD) P/(p-R-T), the “compressibility factor” 1. Introduction Methanol isa major commodity chemical whose heavy industrial usehas been described by Machado and Street? “Thermlynamie chart for methanol have ben prepared by Smith anda Pp surface was correlated by Bhattacharyya and Thodos* In an ongoing sere of reports, fundamental properties were collected by Wilhot etal A valuable sur- ‘ey was presented by Eubank,"’ and a book on the thermo- physical properties was published in Russian by Zubarey, Prusakov, and Sergeyevs."* Palymeriretion of methanol in the vapor stata is a trot Uesome phenomenon forthe experimentalist and correlator. Thishas been examined by Weltner and Pitzer," Tnskeep,® Kel” Tucker Kudchadker,™ Bartcza,# Francs. and Nath” Ta the present correlation of the thermodynamic prop- cxtis of methancl we rely heavily on the PT data of Ma- ‘Shad and Steet nnd om the recent data of Staty © To chore curvatures in Straty's PpT data change sign at & reduced density near 0.83, not atthe critical density. We thus obiain a specific heat C,(p,7), whichis finite a the erica point, via Eq (10), below. Symbols and units are given i the st above, and the coexistence phase disgram is outlined in Fg. 1. Selected Suedspint wae oreo in Tae The pip ome‘THERMODYNAMIC PROPERTIES OF METHANE “Tan Slected Sepia vals for methanol ao 1o1s2s a6 or anto-raatstt~ sa gud 2826 23382 0 ‘perature is from Carlson and Westrum."° Young” reported T, = 513.15 K, P, = 79.59 +0.08 bar, p, = 8.455 mol/L. ‘The only recent determination of critical parameters appar- cently is that of Kay and Donham®®: 7, = 51258 K, P, = 80.972 bar, p. = 8.49 mol/L. ur critical density, p. = 8.40 mol/L, was adjusted in the course of iting orthobaric densities. The boiling-point temperature: Table I istrom Eg. (1) at” = 1.U13 23 bar, ‘nd the triple point pressure is from Eq, (1) at T= T,, Oth- er fixed-pointorthobaric densities are from Eqs. (2) and (3) 2, Developing the Equation of State ‘The present isochori equation of state (EOS) is cone strained to the formulated coexistence boundary (vapor pressures and orthoberic densities). The winnowing of ‘masses of data, to cull inaccurate but often precise sts isa difficult but necessary process. Hence, some excluded data, sre presented inthis report, but ar used with zero weigh for the least-squares determination of the coefficients in fitting fumanain, Tae aclete vsial LOS fo Howadeusy sephoe also is presented below (Ea, (4)]. Apparentiy no high-pres- sure melting line P, (7) has been established for methanol, which forms passes under these conditions. See, however, 8, Carlson and Westrum" for calorimetric transitions at low pressures and temperatures. 24, Methane! Vapor Pressures Some ofthe available vapor-pressure data for methanol are listed in Table 2. Deviations from Eq. (1) are given in Table wing x(7)=7/7,, 2, (7) in bar, and exponent 10. Then ‘Tan Summaryof vapor pressre data for methane, 801 In(P,) =0/x + bert di? ber +f —x¥, (1) where a= —10.752848 790, d= 4373231941, 16.758 206 642, ¢= — 2.381 377489, em — 303424623, f= 4572 198 698. ‘The root-mean-square (rms) relative pressure deviation of 0.54% for 83 selected data snot as precise as obtained for ‘many other substances. Data of Straty® at ID = 99 [ ID) ‘entiation of data souroes] were used before discovering that he doubted their accuracy, based om apparatis iit tions. Thedata of Young.” ID = 10, based on those of Ram say and Young,” are included to provide information on posible temperaturescale adjustments (column 47), ‘which would be useful to salvage tei entesive and precise orthobaic densities and Po data. ‘Column Resid. in Table 3 gives values ofthe residual, Ine EIU) — = BI TIL= B Dade ‘he examination of which s most helpful for developing any ‘apor-pressure equation. 2.2. Methanol Orthobaric Densities ‘Table 4 presents some sources of orthobaric density data for methanol. 2.2, Saturated Liquid Densities eviations ou By. (2 ate give ft Table 3 using x(1)=T/T,, u(T) (1 —2), and exponent B= 0.35. Then ile —D mau + WE = 1) eta? = +a 1), @ where = 251730906, c= 3.066817 68, = 2.466 694.19, d= ~ 1.32507680. ‘The me solative dencty deviation ie 0.170% for 43 selected data, Data at ID = 72 have been obtained from formulated ’D ‘Author/ year ‘Range of 7,K ‘Range of P bar Ramsay, 17 a) esi omnes = 10 Yeunplisio rae 10) oe ours 13 Mandel 1913 (Ret 46) 25-209 Lato“ 13107? St Walter, 951 S38 35-100 SS Kay, 1958 (Rel 32) 3-303 ee © Hits 967 Ret 28) 30473 2s.304 70 Ambrose/Sprate, 170 (Ref. 3) mms) oat 73 Zabasey 1972 Hss10 isa0-or4 1 Gouel 973 (Ret 13) 638 25-10 Th Ghar, 1974 (REE) ae 338 10-10 75 Ambros/Sprake/Townsend, 1975 (Ref. 4) 353-463 1331 33 Machado, 183, 290473 2401 65 Miler, 1988 (Re. 48) 1510 Lag. b10-* 4 Phys. Chem, Ret Data, Vo. 16, No 4, 1907,802 ROBERT D. GOODWIN Table 2 Compara of reported vapor presures with values calultd from By. (1) mF H PeRE £18 Sun 18 20h 13 Gum £18 2m 18 Sg 8 2s 28 23s 8 Ss 18 SES 18 8 1B $8 3 6 ios oh Hess #38 ee SoS ie S22 es 8 ie es ie 3S a 358 es 3 ie ini $B Bee 3B Bs 38 mes 3 ie Se 373 me BB ese $e ies 3S ie 3S ee 2 EB BESe 3 ES Bese 3S S88 3 8 ge 3 EB ess 18 Be ie sas 75 1:00 353:460 HAS ss BiB aS B18 B38 HG Sis wr 0.78650, 1 og02 boaasse 0.46087 :g8409 0°90361 09064 Bi9ear6 olgsier 8.915 0334357 err 0.34935 0°35169 O°se194 633087 o'ses7 0.59122 0° so202 beans 86ea) 0.65988 68082 eset 0.69611 b:shi00 o:s9n10 60086 0.62037 -63012 63988 Ore5s88 o-ssrat 62652 cease O:eas5e 0:70808 0.72898 on 0.78655 0.80891 4. Phys. Chem. Ret. Dat, Vol. 16, No.4 1987 Rss oon 2308 8 ote SSeS oes So sess Sess SB SSR 10.$82466+00 Sess 10.28333+00 Sees Seuss 02183006401 sii Ge F Tae ae ose cee ‘ta 3 0:32204F-05 SRS ERE (0.252435+00 Sasi es Sse 0.984341100 O11 T8absOt SHES! SES! SReeS, SES SERIES Sees Sas seems eee 0.28361E100 Sees Seas SB 3 aay9E01 steseesot ro4esenc2 EReeess2e8 or 0.00746 8.00093, 000254 0.00183 000037 000240, 800267 Bcooet9 0.02468 8.03086 Bloaais 8oae00 0.02577 0203303, 0.02005 0.02572 0.0095 0:0251 b.00904 ocoatss 0:02578 0°02262 o°02172 0.02089 8200880 O-o1e24 0-016 o°01sst ook o.o1s E828228 SSBB ot bgizegeteticcceces‘THERMODYNAMIC PROPERTIES OF METHANE 803 ‘Tate 2. Comparion of repae vapor premure with value aeaitd from Eq (1) Gontued, K te Den B10 aa.190 Dass O.Ay0RREOT 0.01 0.01018 35 1.00 432.920 O.1747gEC02 OLi7476E-02 0.01 0.00881 38 9 M300 O:biegrecea Oc2iendeco2 O°tt 0.00783 75 1.00. 455-270 Ola7is7Eo2 ol2Tisae-02 0.13 0.00621 48 100. 462!900 O:3310REe02 O:32983E«02 0138 0.00515 8 Von assis7 Oisanstée02 O/saoo0E=02 -0.27 000190 3 100 deli Oleate0en2 OlezastEsoa -0.32 B.o0101 9 100. S03133, Olesoizéco2 0:¢89006~02 0.02 0.00086 9 too $03:202 OlenseaEet2 Ole4981E-02 -0.08 0.00063 99 1.00 508.130 O°751386602 0:780296-02 0.14 0.00035 9 Veo Soscuas OL9S12aEC02 OcTS0saEs02 0110 0.00033 0.00 263.180 0,$13%6 0,206688-01 0,209998-01 0.02389 0109 273-180 0.83267 0:39463E-01 0.40521E-01 boa 0:00 293-180 0.87189 0.127998+00 0130148400 B.oaaee 10500 303.180 0159140 0:21332Es00 0,21882E400, 0°00259 009 313-150 0.61091 01347306400 0. 354636+00 0.02215 Blo 3231180 Olea0N1 O1S4129Ee00 Or SSSHOEAOD 0:02087 0100 3831180 Oleaeoa OLi7E79E.01 OctaosIEsOL Oconee 0:00 0.70565 0:25291F+01 0.25849E-01 0.01782 0:00 0.73796 O° 3a944bs01 01383486001 o:o18i7 8:09 074746 O-a7wneE0r O!47993E-01 o.o1s91 8:89, 8:36089 Oce334iE01 OotosiEsot 8201355 0:00 Oce3z20Ee07 OceALAtE«OL oco1a31 8.00 O:10760Et02 0: 108948-02 o:o1078 8.00, O.i37e0E+02 0:13919E~02 0.00985 0.00 B.kessi O.21701E«02 B.a1996Ee02 00682 00 D.g6402 0:26763E+02 0: 27088602 :00552 00 0'90383 o-32e1TE902 0. 331466e02 0°00834 0.00 O:g2308 07397138402 0:40N20E002 0:00289 0:00 (0196208. 056759002 O"s79asecoa “2°03 Oloaoa 0.00 Ol9TIet OlerTaaEeon Olea2a7E«03 “2.38 -0.00029 0.00 0198156 O.ez213ee02 Olea920E003 “2.48 “0.00078 0.00 0198547 0-69597E403 0.943180 2.41 0.00090 ceo Oiga937 O:9i9iaeco2 0:73990E.08 “2°84 “bc00TTa 0-00 (0.99527. 074159002 0-T6MoEs02 “2.86 -Ol00144 0-00 0.99522. 0.78987E+02 O.77647E~02 “2.14 “0.00108 0:00 0.99717 0:76762E+02 0.789956%02 “2160. “0.00154 00 Dl99a1s Ol7rresEeo ctaKuaFena 2/46 --not ay 0.00 0199912. O.7agiseeo2 OsA0saeEs0 {o%oo1a2 0.00 0.40139 0.13600E-03 0:12149E-03 0.0264 0.00 (0:14670E-03 O:14408E-03 6125 0L01304 0:00 (0:221306-03 0:212618-03 4109 0.01910, 0:00 OLta16? O1}8aI0E-03 OL3EsMME-03 T1396 O.o198) 0.00 (0142685 0°505305-03 0-S0081E-03 1.00 0.01962 0.00 221.250 0.43162 0.684605-03 0.65127E-05 0181 0.01997, 9:00 228.080 0.43904 0.935905-03 9501990 8:95 2Beces0 0:43N6 Octobsoe- 08 ‘0:89 0.03038, 9.00 228.780 0.44625 0:131505-02 0113437E-02 2.13 Ov0a002 (0100 313:100 0.61081 0:34664E«00 O135281E00 2.03 0.02m18, 9.00 327:800 0.63968 0.666618-00 O.68104E00 2.12 0.02082 8:09 362.480 0.70086 0.283008-01 G.2s28sE001 “0.25 0.01709 {7 0.00 368.780 0.71957 0.304996+01 O-307I7E101 0.71 0.01698 7 0,00 375.680 0.72893 0. 35s6sts01 Ol3shosEs01 0°95 B.o1e22 7 0.00 398.350 0.75761 O"ssa2REs01 OlssB8Er01 “1.18 8.01416 6 0.00 412/280 0.80425 O:fo4neGv02 O-YossoE02 2/10 001099 67 0.00 414.080 o-80774 0-109190002 O.InM4ake02 -2/07 01017, 67 0.00 326.880 0.88272 0.14824E+02 O.15192R+02 “2.42 0.00825 67 0.00 444.380 0.86686 0.22180E102 O-22s01E02 -143 000648 SF 0.00 449350 Olsne61 O°D4G32E.02 casoadecna “1°57 Oco0srs 7 0.00 453.880 0.88539 0.2706aEto2 0.27479E102 “1°51 0.00520 167 0.00 438.080 0.89588 0.29SI6EI02 0.29936E102 “1.40 0.00473 4. Phys, Chem. Ret. Dat, VoL. 16, No.4 1987804 ROBERT D. GOODWIN, “uble 3. Comparion of reported vapor pressures with values ealeulated from By. (1) Conte = 3 m7, F Ge PR Reka k tr tren F000 aaa 080 0.90199 0. T1R6REOD “as 0.008 0.721 GF 0:00. ae9.250 0.91513 0.368626002 0.378346002 “1.21 0.00348 “0.698 67 0.00 472.680 0792206 D/3935SEx02 OL39EEIEVOD “1122 0.00307 0.643, 33 0.00 178-400 0.34218 0/18870E-05 0°37744E-05. 8.00322 0:38 73 0:00 180.000 0135113 0,39090E.08 0.372268-05, 0.00868 0-321 73 0:00 200.000 0139017 0.62740E.04 0.6063SE-04 .01s00 0.279 73 0:00 210000 0/40968 0/20350E-03. 0.19971E-03 O.o1e26 0:26, 73 0.00 220.000 0.42918 0.S4810E.03 0.57421E-03, 0.02078 0.239, 73 0.00 230.000 0.44869 0:18390E-02 0. 15085E-02, 0.02261 0.220, 33 0:00 240.000 046820 0:26870E-02 0:36013E-02 0.02386 0.183 13 0.00. 250.000 0.48771 0:81890E-02 0.809455-02 0.02469 0.149 73 0,00 260.000 0.50722 0:17000E-01 011687SE-01 0502509 0.108 73 0:00 270.000 0132673 0130970E-01 0.39134E-01 0.02819 9.063 73 0,00 280.000 0.36874 0:109408+00 9. 1095H5400 0:02460 -0.030, 73 0:00, 300.000 0138525 0-18600E+00 0.186555+00 0.02406. “0058 75 0,00 310.000 0.40476 0:30430E+00 0.308748=00 0.02330 “0.089 73 0.00 320.000 0.62427 0-481708+00 0.484196400 s.03248 “0-116 73 0:00 330000 Dcea38 O:78950E000 OcFESARESO ocmatst “02138 75 0,00 340000 0.66329 0-11044E101 0.110996401 0.02082 “0.128 73 0-00 3505000 0.68279 O.16082EV0! 0:16153E+01 0.01943, “0.121 75 0:00 340000 0.70230 9:22480E01 0122990E~01 oo1826 “0.114 73 0.00 380.000 0.74152 043570801 8.436700) S.o1ssi 0.076 73 0-00 390000 0176083, O°se4s0Ec01 0/SASERE-O1 oorees “0%085, 73 9100 400.000 0178034 c7roaaEso1 0:77338EC01 olor30e “0147 73 0:00 410.000 (0:100006«02 | 0:100sKE«02 oiotiss “0.225 73 0.00 430-00 O:6260e-02 0: 16346E+02 00890 “0°239, 73 0.00 440.000 020400002 0:20471B402 0.00767 “0.158 73 0.00. 450.000 0°2s300Ke02 Ocasa6kE02 S068 “0.127 73 0:00 460.000 0: 3108002 0°31153E+02 500520 “0:085 33 0:00. 430.000 Oc31a00E-02 0:30e7sEV02 8.00396 “0.108 73 0:00 480.000 (Oraser08-02 01457150402 00280 “0:124 73 0,00 490.000 0.95591 0:s46s0E-02 0.547930%02 O.00172 20:16 73 0,00 $00:000 0197512 0.651700«02 0.652855+02 00081 83 0:00. 296.150 O.S8i64 0.16900E000 0.16957E400 oco3ai3 83 0.00 318150 161091 01383008000 0. 384638+00 oLea307 83 0.00 3251180 oLe30a1 0583008400 0:555995400 o-a2218 55 0.00 333.150 0.64992 0841005400 0. 84891E400 o.02119 83 0.00 383.180 O.gs4o4 O:18010E001 0. 16091E.01 0-01905 85 0.00 365.150 0.70845 0:25460E001 | 0.255096%01 0.01789 55 0.00 375-450 0.72796 01352408101 0. 383486601 01665 $3 0:00 343°150 o-74746 oua7e93E-01 §3 0:00. 393:180 8:76099 Biotasiecol 483 0.00 403-150 0.78648 0-837605401 O.AaT4lEe0] 83. 0:00 413-180 0.80899 0-10834E+02 0: 0R946+02, 4830.00 423-180 0182550 OL13Ra3E002 B.13919E002 00981 “0:229, 83 0,00 443.180 O.seusi O.2185s5102 0.219268+02 o0or? -0.150, 3 0.00 455-150 0.88402 01270245402 0.2708SE+02 900603, “0:109, 830,00 463.180 0.90383 0:33083E402 0.33146H+02 200880 “0.097 3 0.00 473.150 0.92304 01401376102 0.402200402 0.00389, “0.109, WS dee pein, mar devon OR 1D cose: "GLO Young (18) Mandell (S1) Weta, ($5) Kay, (64) Stat (6S) Mie, (G2) Hea 70) Ambra’ / Spake, (11) Gitar, (3) Zaberer (74) Coun G5) Ambrow 1 Spake / Townsend, (83) Machado, (9) Stats. «4 Phys. Chem. Ref, Data, Vol. 16, No. 1987‘THERMODYNAMIC PROPERTIES OF METHANE 05 ‘Taaue 4 Suramay of rthobre des data for methane “Kary 7 (Ret 53) 7s ‘Your, 110 (Ret 70) 263512 Vas zubare, 983 a0 abate, 1973 (Ref. 78) Machado, 1963 (Re 42) Via aca Tab, 1988 195-489 Via Ge (7) dt, 1988 bens Via Sty, 1985 S63 {sochores, obtained in turn from formulations of the Zu- ‘barev” isotherms, Data at ID = 85 are obtained from Tait, ‘equation formulations of the isotherms of Machado and Street! ‘2.2. Caturated Vapor Donation ‘The computation of AF along isotherms via Eq. (9), ‘using EOS Eq, (6), involves a leading term forthe saturated vapor at T. (p) for each density along the isotherm, Good- ae= [er o(Z— +92, On \whereit is important thatthe integrand approach zero in the limit of low densities. Our earlier formulation of the satu- rated vapor densities py, has been used for various simple fuids, eg, Goodwin, but is not suitable for methanol. Hence we have used Eq. (3), where x(7)=T/T., u(T)= (1 2), f= 038, In(p,/pe) =a = I/x) + bu” Hews di’, (3) and a= 10619 668 50, ¢= 3.818 45421, b= — 255668202, 795 $67 52 For $3 selected data in Table 6 the rms of relative deviations ‘Above the first blank line in Table 6, we derived the ‘vapor density data from experimental heats of vaporization ofthe named authors (ID) via the Clapeyron Eq, (17) using ‘Eq, (1). us our derived hens ot vaporization m8 able 16 ‘will have the same accuracy (with respect to experimental data) as theft ofthe vapor density data in Table 6. However, Gt T= 00, date ave fram fitting one Kqnid entvopie ana experimental C, (7) data simultaneously [See. 3.3(c)]. Given the formulated liquid entropies, S,(7)/ mol K™, then the vapor densities in mol/L are aD 00 (7) {SDS}, Ga) a where forthe vapor at these low densities we have approxi- ‘mated S(D=S (1 + RinlP/P,(T)} (3b) API = 10 in Table 6 the vepie dentine ee tained from the Beatte-Bridgman EOS of Lashakov” with Eq. (1). AtID = 68, data are from virial Eqs. (4) and (1). At TD =72, data are from formulations of our derived iso chores of Zubarev (Table 9, ID =90), and Eq, (1). At TD = 99 we used individual representations ofthe Straty® pseudoisochores, with Eq. (1). Many deviations in Table 6 fre unacceptably large (ste Fig. 2). Derived heat of vapori zation depend directly on these vapor densities via Eq, (17), In the last column of Table 6 under F(z) are given experi- rental values of (Z, ~ 1)/(Z_ —1)- In the limit of low densities, one obiains from Eqs. (1) and (3), Z,~exp—O13T,/T,), ie, Zp=0 in this limit, T.(9)=0. Te fans feat i in wah a BRSSEERISREEISSSES ERSSIERRSEERSSELESSELESESESSERSESSERIERSES Biseseeccece: a5: 2 om oa e288 3 peceeesrssoessoess sobsroossoosssossoosshobooobbosososetasioa| S 12 o.oo 3p3.130 Rt i “ocoae “4. Phys Chem. Ret. Data, VoL 16, No.4 1987808 ROBERT D. GOODWIN ‘Dive S Gmperna of recat tute geld cease, ‘Sitti By 7 Canad Z salt Dee_ (onic 3s os ies Ber bia aasceseassaecsisecsessecsiaeseiesscsseessessesiss SEEEEE: 3283 $8888:8283 8 8822388 1 ese: "CD Young. U8) Kas.) ROG / zune, (3) aba, G9 Ati 6) icads ex ae ‘L.Phys. Chem. Ret, Data, Vol. 16, No 6, 1087‘THERMODYNAMIC PROPERTIES OF METHANE ‘Tle 6 Comparion of reported saturated vapor dentes with values eluted from By. (3) Dw Fo, > Ge, 8 aan A) K nan ni” ews Cani/IVE Gand 3.00 313.106 0.610810, 140348-01 0. 14074E-01 -0.29 06196608 0.96843 0.04080 31200 Sa7'900 0.63965 O-2610sE-01 0.26153E-01 “0119 O-10426-02 0.98604 0.05864 31200 337400 0.65899 0. 3H2R1E-01 0.383206-01 10.10 0.14336-02 0.94732 0.06807, St 200 H3‘t00 O6iasi Oc140436-01 O:14074E-01 10/22 OL6196E-03 0196780 0.04160, 512.00 327.900 0: 0.260988 01 0:26183E-01 0:22 0.1042E-02 0.98730 0.08817 Si 2.00 337's00 0: 362236-01 0°383206-01 0.25 0.1433E-02 0.94876 0-06621 24 2.00 306.130 0 :103S8E-01 0130274E-01 “0°30 O-4753E-03 0.97151 003681 4280 isos0 Oigtaer-or O:19reae-o “0-01 Ocgna7E-03 0:90081 O0sI38 24 2.00 330.860 0. 8.290S3E-01 0:29080E-01 0:01. 0-1137E.02 0.95284 006098 24 2100 337-610 0.65862. 0.36052E-01 0/38049E-01 0.01 0.1424E-02 0.94616 0.06918 38 2.00 6.130 0. O°102836-01 0°102766-01 0125 0L47S9E-03 0197179 0.03645 7 2.00 30°s60 0. (0: 200688-01 0:200806-01 0.06 O.11378-02 0.98238 0.06187 45 200 ariew 0: (0 3807SE-01 0:38089E-01 0.07 0.14248-02 0.94589 0.06992 ye 100 do8.180 0. (69900102 0190273E-02 0°80 013446E-03 0.97880 002803 26 200 33.180 0.61091 O-14041E-01 O-14t0se-0 “0.46 0.620%E-03 0.97008 0.03871 te Fo Maso: Didanave-o1 Oldaraae-o “0136 OLIRME-oa Ol9shie OL0c0S? 2 2.00 337.880 0 (0:36287E-01 038392E-01 “0.27 0.1435E-02 0.94890 0.06603 46 200 ds.i80 0 46661801 01466536-01 0.03 O.168BE.02 0.94078 0-07682 3 30.00 378.390 0 O'197I2E-06 O11270RE-06 0.03, 0.2029E-07 OL98R98 O.014Re 30 30:00 200.000 0.39017 0:369268-08 01369496-05 -010g OltuziE-oG O.98r47 0.01619, 5 30:00 325.000. O°s10096-04 0:510576-04 20°02. 0:4704E-05 0.98598 001811, 3 30100 380'000. 8°39S91E-03 0/39S648-03 0107 0.24998-04 0.98388 0.02090 5 "190 31s!000. 0 o!goae7e-02 108 O.1192E-03 L980 0.02582 30 Leo 3s.000 6. O:251a6E-0F O12527SE-01 0°55 G19498-03 0196279 OL04808 69 1.00 300.000 (0.763008-02 0.768998-02 -0.78 0.37198-03 0.98020 0.02558 $8 1100. 30s:000 (0.968005-02 0C97Si0E.02 “0.73 Ol4s47E-02 0.9728 0.07936 100 HS!000 ‘O:ts2008-01 0:182948-01 “0.61 O.66448-03 0197042 0.03829 6 190. 320000 (0:188505-01 0:189346-01 “0°55 0.794HF-03 0°96645 0.04535 6 1100 52s:009 (0:231606-01 0123275E-01 “049 0°94498-03 0196221 004883 § 100 330'000 9-283008-01 9-28419E-01 “042 O°ILITE-02 0°95142 0-08802 B13 H888. O:B3eoe-o1 Oc3kasce-or 70°35 O:1512E-03 0°95150 OcOeies $8 1100 Mo!000 OL4tse2e-01 “0129 OLissae-o2 0194697 0.06853 6 100 34s!000 (0:497506-01 0:498646-01 70°25. 011784E-02 0.94110 OLOTEIO & 00 so'o00 8°593608-01 oLspe7e01 “0'19 OL2066E-02 0:33e0y 08387 § 1500. 340:000 O:as240e-01 OcesseoE-01 70.14 0.27366-02 0.92190 0.10092 ° 345.000 -97870E-01 0:98009E-01 “0.14 O°3181E-02 0.91481 011008 ° 370.000 114S6Es00 0-11474Es00 “0116. O13571E-02 0.90739 0111966 ° 435.000 153536:00 01133806400 “0120 014060802 0.69967 9.12968, ® 385.000 0179326000 0179936000 “0.34 0°520SH-02 Olk8a06 | OLISIIT 6% 1100 390.000 ©.20669E-00 0:207595+00 “0.43, 0.S673E-02 0.87416 0.16261 6 1.00 39s:000 0237466600 0123877E000 “018S OleeI2E-02 O.Bo481 OL17469 % aorses ©.206148-01 0:20727E+01 “0°55 0°S8196-01 0.56800 0155891 o 00 tanlon Olbstasero1 Ol2ria0E0; "0:03. O:S44SE-01 O:Se087 | 1SeTa 99 2.00 490.940, O:269116:01 1267 14E001 O11. O.7496E-01 9.50720 0.63677 8 97-198 0,32855E¢01 01321756101 0°50 0.9999E.01 0.46525 0.69099 98 2100 s09738 (035596601 0387185001 0148 OL1A13E,00 O.4n091 0.74427 9 200 s0425 OLASESHECOT OLASHATELOT -0oq W'3IaRan Oo taaM Aaa 10 273.180 0.53287 0,17S398-02 0.161835-02-3.54 0.1084E-03 1.01726 -0.02231, 00 00 00 0 00 00 ‘o0 0 0 0 0 0 10 283.130 0185236 0.310848-02 0.322436-09 “3159 OL17M4E-03 tlotsas “0.01970, 10 293.150 0.57189 0.528996-02 0.34734E-02 "3.36 0.2767E-03 110098) "0.01308 10 0.00 313.180 0.61091 O.13713E-01 O-14i0s6-01 “2.78 0.6209E.03 Ol9oaa4 OL00873 10 0.00 323.180 0.63041 0:21032E-01 0-2158i5-01 -2.5§ 0.8469E-03 0.98391 0.02079 10 0.00 333.180 0.64992 0:31396E-01 0-321236-01 “2.26 O.tn97E-02 0.97269 0.03899 19 0.00 343.150 0.66943 0.4S721E-01 0.466838-01 "2°00 0.1688E.02 0.94013 0.08182 wo SSS'1gU Uleuave Oles0svE-01 Oles287E-01 “ise Ol296HE-02 L947} B:0st08 10 0.00 343.180 0.70848 0.907248-01 0.92358E.01 “1.77 O/2980K-02 0.93268 0.08699 10 0.00 373.150 0.79706 O.124346+00 O.12646E600 “168 OL2873E-02 O.916%2 0.10813, 10 0:00 363.150 0.74746 O°1677HE00 O/170S1EC00 “160 0L4975E-02 0.89793 0.19189 807 4. Phys. Chem, Re Data, Vo. 16, No.6, 1967,808 ROBERT D. GOODWIN ‘Toble 6 Comporion of reported saturated vapor densities with values clelated from Bg. (3) ~ Continued Dow Tm ? Ge, % Gar 2D) x mov moi ber Gal VR Ce iw 393,180 0.76697 0. 222HBEV00 O.F2680E00 1.72 0.6550E-02 0.51909 0.156253 io 4031180 0:78648 0:29271E+00 0:29813E000 “1182. 0.7993E.02 O.8S7SS 0.18403 213150 0780599. Oa79S0Ee00 0138794600 453/150 Oce4so1 02622300800 OL641495000 4431180 O:86451 0.765336100 0.818085100 453.150 0188402. 0.99431E.00 0 -10403E001 S350 O:S2s0e 8.13naREIOF tee 2EAOF 01942ss O:2oastEDL O.21716Ee01 0.96206 0°249498401 0: 265096+01 498-150 OL9TiRL 0313026001 0.33150S001 508.150 0.98547 0398836101 0.424908401 507-130 0.98937 01430996401 0.463705101, 18 0-10048-01 0:83570 0.21230 ‘99 0.1874E-01 0.78388 0.27927 (64 0119956.01 0.75185 0131697 192. 0124048-01 0.72299 0138704 13 0.4163E-01 0.64850 0.45806 28 0.S6818-01 0159243 0.52665 47 0°82296.01 0152431 OL61486 ‘57 0:1051E-00 0.48768 0.66200 30 OL139Es00 0142606. OL74162 (0S 0:2179E:00 0.40603 0.76781 10 509.130 0.99327 0.469695401 0.814835401 “8.71 013008500 0.38394 0.79605 10 $11-180 9199717 0°s24eze-o1 0°593636.01 11.62 O°S499EA00 0.38491 OcAtaKe io 3115680 199613. 0:S5e8zE%01 Oce28isetoL “10:89 O:AS45E-00 0738534 OcaSBes 0 ‘512-150 0,99912 O-SH610E401 O-671645+01 “1274 O-1227E001 0.32186 0.87627 20 275.150 0153267 0.176088-02 01481835-02 -2.06 O11OR4E-03 T-0019T -0.00046 20 3831150 0155238 0.318396-00 0132243E-02 “1.28 011774E-03 Ol9ait6 oL0tt42 20 0.00 298-180 O-sbiek O-698186-02 O.70273E-02 “0.68 Bata4Gl-d3 0.99973 O.02819 20 4303-180 0.89140 0-S5858E-02 01893986-02 “0163 O-422SK-09 0.97722 0.02944 30° 0.00 3131150 O-g1091 0. 140266-01 0. 44108E-01, 0.99106 0.03740, 20 0500 323.150 0.63041 O-21449E-01 OL2TS8E-01 0:9647s 0.0455 x0 33972880 0.68909 0.36148E-01 0.383928.01 0195236 oc06i5s 2 3431150 0.66943. O.46476E-01 OL46653E-01 “0138 DLI6RHE-02 0.94482 0.07169 200.00 353.180 0.68894 0.660220-01 0.66287E-01 “0.40 0.22618-02 0.93520 0.08631 Fy 4363-180 o0-7oues 0.919824 01 ol923ssE-01 “044 0:29808-02 0:92022 0.10309, 20 0:00 3931180 o:72I96 O!1asraBe00 Os taeseEs00 “0°57 B.3ATSE-02 0:90608 | 0:19139 20 0100 363.180 0.74746 O:16943Ec00 OL170SIEC00 “063 B.497SE-02 OL88918 0.1409 200.00 3931180 0.76697 022482600 0.226805+00 “101 0.63308-02 0°87271 O-16448 42031150 OcTeeae 0°294420000 0294136100 “1124 0°79996-02 O°8SRSP O1290e8 do ox O13580 OL aazenEv00 2:55 011257E-01 O!61in2 0.24381 20 Oce4S01O.gaz0eE00 3103 OL1s7aE-o1 OL7geis 0.27867 2 0.86881 0.766108+00 0:81808E+00 “3.66 0.1975E-01 0.75508 0.31648 Bo 8:s8402 OcepnarEgoo Bctowoamvar “4:52 .aaya-o1 O.7asN4 0.38097 2 4731180 0192304 O.19R02E01 O46472EO1 “4.34 OLAL6IE-OL 0.64700. OLaSbid 20 493.130 0.94258. 0.20282E101 0.21716E+01 “6.74. 0.S641E-01 0.59532 0.82290 2 4931180 0,96206 0.266S1E+01 0.26509E+01 “6.52. 0182296-01 0.53016 0.60710 $021180 ol9eise Oltei2ierot O-teorrot “a.11 pvtesmEon O4scae 0-902m2 $09:000 Oc5805e B:eagorson O:3ransEson 14:95 S:pesaecog O/t9G38 | OcISteL (0539009 0:39%408400 0151324800 “Sloe OLEMIE-GE OLa8225 O.1S2I5 (:79984 0:339108400 0.3s742Ev0O “5.13 0.9349E-02 0.87008 0.16787 (0550960 0:38s708400 0'a06PiEv00 “5.21 O-1047E-01 O.85739 0.18428 88388283888882283332338828282228222223223222322823323282823288232825 » 0162911 01496408100 Ols2ea0E00 $132 OLISILE-OL OLfso18 0.22072 » (083886 0:561905400 0:59364EV00 5.35 O-1466E-01 0.81368 0-24075 » 0.4861 0-635905000 0167122E+00 “5/38 OltestE-O1 0.79722 0.26203 2 (0.85837 0:717708+00 0.75607E+00 “5:32 0-1837E-01 0.77967 0.28470 » 0.89748 Olb1470E-00 Ols64eaE~0o “lie OlaaISE-O1 Ol74i23 0.33437 » 088763 -t03298-01 0.10875E+01 “5:02 0:2607E-01 0.72002 0.36177 Bo. 0.49739 oLit674B:01 0:12261E401 “4.79 0-2846E-01 0.69729 0.39115 3 Sisnead Gcldgsreot G.iselercor "2.97 Qcaaiee-ol Ocewene 0.49707 0. 092665 O:170SREVOL 0°176626001 “3.25 0.438BE-01 0.61715 0.49470 » 0.93640 0:19597E401 O:20007H01 “2118 0°S097E-OL OvSRUST 0.83688 » 0.94616 O"2a723E40L O.a979AEVOL “0131 OLBDOSE-O1 O1Skeed O1SKS82 2 0.96867 0.35755E101 0.30097E+01 18.80 0.8953E-01 0.40670 0.76663 5s 53-144 188409 01303605601 O104FREs01 +0180 012496E-01 0.69423 0139497 55 4631188 0190361 0:12660=401 0:152386+01 “2.86 O.S191E-01 0.66977 0.42671 58 S73:195 0192312 O.465208401 01168900001 “3137 OL416BE-01 0.62691 0.48209 “Phys. Chem, Ref. Data, Vol 16, No 4, 1087,‘THERMODYNAMIC PROPERTIES OF METHANE 809 “able 6 Compurion of report strate vopor censtie with valu ceuatl from Eq (3) ~ Coninued > 7 7, 7 Ge; 8 afi a @ K out mov Devs CoV Ce) E000 Gas. T 0.pais O.DOHNOEOT O.ITaEO —-3.A 0. S680E-O1 0.57703 0.54684 S5 0100 493.201 olsezte O-a7e60EVo: D.2EssiEs01 2.07 O.2e7E-01 0.50875 0.63865, Shion Sos'ane Ol9at6? Oc38a90Ee01 0.99389E001 2.54 0.1468E000 0.42048 0.73720 & 0.60 an0s000 0:74084 0:27199EV00 01273855100 Octasaeon 0.85095 0278042 69 0.00 405-000 0.79009. 0.31069E100 0313248400 OLe34TE-02 084451 0.20082 §9 0100 #10:000 0.79984. 0-38403E000 0357426400 O193496-02 0.49339 0.21528 £0100 418:000 0:40960 0:40255E+00 0: 406PTE400 OioaTE=-01 082180 0°25065 & 0100 f2sio00 Olszent olsive7Eon 0524306400 OL3itEOT O:79481 0.26514 & 0100 $30:000 0185866. O.sHb44E+00 0.59364E+00 O!1a66E-01 077963 0.26478 $0100 438-000 O'sas6t_O-ges90=00 01671228400 Bi6trE-01 0.76387 0.30641 6 0100 440.000 078887. 0.75200E¢00 0.75807E400 O!1es7E-01 0.74411 0.33068 © 100 fasiooo Olsest2 Ccass2eEs00 0:65S396+00 Sipoe0E-ot O:92394 | 0:35826 69 0100. 450.000 0187788 0:9717IES00 0964636400 O°25is6-01 069774 0.39086 & 0100 455.000 0188769 OL1TL49ECOT 0. 1087SE001 0°2607E-01 0.96707 0.43019 68 0100 460-000 0789759 0130205+01 0.12261E-01 O.2o4gE-01 0.03519 9.48431 30 0.00 398.180. O-S8ie4 0-670008-02 0.70273¢-02 O134466-03 0178604 0.27621 70 0100 325-150 0.68083 O14S700E-01 0. 25816-01 0°88696-03 0.45280 0.70707 7 0100 323-180 0.63041 0.44600E-01 0. 21881E-01 0° s8696-03 0146397 0.69268, Ho 8:80 MACISO GcGrone OcEsrarso0 OcSeroaecor Octbsnecos Olea O08 70 0:00 348.150 0.67918 0.80S006-01 0.387846-01 Ol19se8-02 0.64788 0.48800, 300.00 13.150 0.72796 OL1sTHOE00 0: 12646E00 0°38936-02 0.72475 0.35566 30 000 313.150 0.72796 0-16070E00 0.12646E+00 0!3e736-02 0.70897 0.32606 30 0.00 394.150.7761) O-tansorsoo 9: 26099E000 Scftise-o: O:60081 | 8241032 30 000 398.180 0.77673 0-312008400 9:26039E.00 O'rise-c2 o.sia12 0130199 30 0.00 425.150 0.82880 07SHS70E=00 0: 5003sE.00 01125701 0.66614 0.43399 7 000 423.150 0-82580 0-Se4B0E=00 0: $003SE000 OL1DSTE-01 0.67682 0.41795 30 0100. 4481150 0"87427 O:s6s90E-00 0:92272E400 olarve-o1 0.35527 0.31882 Zo 0.00 473.150 0.92304 0.AS9S1E601 0.168726001 O:463E-01 0.64095 0.46395 3 O00 473.150 0.92304 OL1sSisé=01 0.16872E01 36-01 0.68896 0.84068 Ta boo fa2.4st_O-82491 O-Soo00E~00 O:496808400 96-01 O-7a618 0.27629 72 Olo0 480.407 0.93720 0:200008+01 0° 20236E+01 Oisteae-o1 Ols7685 Olsin6 F2 olo0 4981197 0.96591 0: 3o000E.01 0° 30281Es01 Ocbo07E-01 148568 0.65159 T2000 $04%6i5 098042 O-40000E01 0.81583E001 “3.81 O.1653E+00 0.42109 0.74808 2 0500 $09'433,0°99380 0-Son00E01 0°s2298E-01 “4.39 O.387ExO0 036214 0.52421 B bio S387 0 S000NE+01 O-6Rs10E0L 12:17 Octasievor 9.31481 9:88837 Ta 000. $12.240 0.99930 O-POOD0E01 01683596001 2.41 —O.1429ENO1 026985 0.94347 73 0700. 1751400 0.34218 0.129395-05 0°125296-08 4195 0.1966E-07 0.94270 0.07405, TS 0500 140.000 0.38118 0.260946-06 0.281586-06 3.72 0.39926-07 0.95522 0.06046 T2 bo0 200.000 0139017 OL3T7ONE-0S O.39949E-08 2103 O.aaDIE-O6 0.96718 OLouaut 13 0:00 710.000 0.40968 O-11648E-04 0.{1480E-04 44 0.1233E-08 0.97239 0.03568, 73 000 220.000 0.42918 O.J21SiE-O4 OL3iss7E-0€ 0198 O.308KE-05 0.97638 003082 TS 8:00 H0:000 cktaso Octewssees Octoeecos ite Oarse-oe Oseuee lone 73 000 250.000 0144771 0.3949S6-0) OL39souE-09 | -OL18 O12879E-O4 0.98624 0.01778, 73 0.00 260.000 0:50722 0.790296-03 0.795786-03 “0.44 0.5288E-04 0.98715 0.01563 T3000 270°000 0752673 0:14911E-02 0.1s0s0E-02 “0-81 0.9901E-04 O.989R 0.01312 33 0:00 380:000 O-Ses74 0:460486-02 Ondesseeced “1.06 $.2427E-03 8.96701 8.01679, T3000 300.000 0158525 0.76212E-02 0.76899K-02 “0189 O.3719E-03 0.9813 OoasI2 73 0-00 310.000 0.60476 0.121626-01 0:122618-01 70.80 O-SS16E-03 0.97529 0.03193 T3000 S20\000 0162427 0:187H96-01 O.189s4E-01 (0.97 O.7948E-03 0.96856 0.04063, T3000 Ho‘000 8156399 OL41aR9E-01 O.AtséaE-oL “0137 OL1SSeE-Ua 0.90767 | 0.06782 T2000 30°00 0188279 O1S9B77E-01 OLsB876E-O1 “0117 O:2086E-02 O/9n482 OLonaz2 73 0-00 360.000 0.70250 0:83179E-01 0-633408-01 “0.22 0.27301-02 0.92288 0.10004 T3000 370°000 0.73181 O.A146HE=0) O.TT47KE00 “042 O° 357NE-U2 0.90699 0.12019, T3800 Mo‘o00 ols4is2 OLtsussrsoo o:tss4ses00 “0:38 OcaooxE-o2 8.89940 O:13903, T3070) 390.000 076083 0:20641E«00 0:20759E00 0°37 0°SRT3E-02 0187536 0.16106, T3000 400.000 0.78034 0.2 7ORDE00 O.2THESEC0” “133 0.7452E-02 0.86060 0.18012 73 0100 410.000 0.79984 O-34948E+00 O° 35742E+00 "222 0.9349E-02 0.84426 0.20127 Phys. Chem. Ret. Data, Vol. 16, No 4, 1967,810 ROBERT D. GOODWIN CComparion of reps saturates vapor semtes with value clelsed om 5. Contin Sistas ea oe K Pan tae evan Coke Ge) B 00 430.000 0.575816+00 0.59364E+00 -3.00 0,1466F-07 0.79403 0.26614 8.00 t:00 Ocpuaaiven 998000 33 Octane 6.26008 6:30950 33 8.00 $o:00, Ociisecioy Octgzeiziy 3143 blame! 6.58508 6.40596 Boe Olsteas o:t3isolo! GciseloEvo! “107 Olaniek-o1 OcerTB4Olasise Boe Clases ocaooctcor G.200nTEo1 “O-tt O:S0yTE-ot O.shsrOLssaat Boe flgsgor Blansstsor O.2e083E001 4.08 OLAHIOE_OL OLavERROvesiT9 Boe 0998 Orisercor S:assearor $35 octtrttoeo Ocdtaee | O'Seuae 130.00 Sto.o90 0.99495 olsuaveico! OlseaeTEror 2.83 0.36600 OLMSID 0.8459 35 B.a0 Stocens O:9ms8 ovsuinercot o:saas9erot “1°39. OL3omoteo OLaeis6 OL8SRt ID cle U3) Yong GO) Tan 1) Pek, 9) Lata, 4) Svs, (51 ter.) Ks (Gm w/e. 0) Resets (2) Rue, 1) Babe, (9 Canal {95} Eotnt gy 8) Ste 0) wy OB) Se 224. Aternatve Vapor Density Equation 23, The Virial Equation Atter completing the present report, we reinvestigated ‘the formulation of saturated vapor densities to obtain Z, 1 .45p+0. The argument is temperature, T.On integrating Eq. (2) along ieotherme wsing EOS (6), however, T—T,(p), P= P,|T,(p) for Eq, (2a), and then the argument is den- sity, p.In either case, symbols refer to the state of saturated vapor at coexistence, where xs /T,, use(1—x), ZmP/ (PRD), B= 035, Z=1+Z—Depl foo), (Be) fx) =A) + Ag? + Ga Ay= 770276242, As— 270.449 459, Ay= —0.797 4016, dg= — 600.239 197, A= 732613113, y= 887067221, Ag= 51.823 5057, ‘This equation yields Z- the limit of low temperatures. ‘For the inal equation of state, Z(P,p.T) =1+ BUTI + (Tp? +5 “ we used 18 mixed FT data from Kell” and from Kud- chadker?” at 298 to 573 K, to formulate B(7) in L/mol, using x(7)=7'/1000, Bs Bs, Ba nr) =A, + Fs By Be, a (Ty =I Fe Fa Bs 4) By= 36922, By= 1.3088, By= — 43214, B,= — 0.015 008, with an average absolute deviation of 0.021 L/mol. Corresponding data for (7) in (L/mol)? have been formulated graphically, €(T) = — expC, — (7/1001, C= 17.1634, y= 4.4545, For methanol, C(7) always is negative in the present range of reduced temperatures of 0.58 to 0.97, quite in contrast to simple substances. (40) sl. oevaton of sueind Vapor Dat . I ion Gemiasea voce : * g Seco a tas © Zubavev O40 eae eI sr © Lashakov coo 4: Phys. Chem. ef. Data, Vol. 16, No.4, 1987,‘THERMODYNAMIC PROPERTIES OF METHANE 2.4. Pressure-Density-Temperature Data ‘The location of available FT” data for methanol was plottedn 1 coorainates by Machado and Street. Recent data of Straty® along isochores (at densities from 0.25 to 2.62the critical) extend from 378 to 573 K at pressures from 26 to 34? bar. Soneres of data ate given in Table 7. To ‘obtain least-squares coefficients of the EOS, we used 164 data of Machado and Streett"; 220 data of Straty**; and 16 low-density data generated by virial Eq. (4), above, which ‘constitute 400 points from more than 1606 available data points. The vapor pressures, Eq. (1), and the orthobaric ‘densities, Eqs. (2) and (3), also contribute to the EOS as ‘constraint. ‘The PpT data of Zubarev and Begdonas"™”* were given first asraw data (with some typographic errors), and then as smoothed tables. We corrected the raw data errors where possible and arranged these data onto isotherms. Each iso- therm then is represented by a polynomial, in which the number of terms n were selected: 6) ‘where o=p/p, isthe reduced density. In Table 8 we give 7, Pry Z, Zs a0 the aTerenves ut Zh pereeut, The coed cients, are given atthe top ofeach isotherm in Table 8. By reading these isotherms at rounded densities, we obtain the isochoric Zubarev data given in Table 9 at ID = 90, 2.5. The Equation of State An outline ofthis FOS was given by Goodwin # At [present (see the Introduction) the specific heat C, (p,7) is finiteat the critical point. The following isochoric EOS gives pressure asa function of temperature along paths of constant density (isochores) which originate on the liguidvapor co- existence boundary, specified by vapor pressure Eq, (1), and by the orthobaric densities Eqs. (2) and (3). For any iso- ‘Tame 7. Summary of Po dat for methanol ait chore (density) the coenistence temperature T, (p), as found by iteration from Eqs. (2) and (3), and thus the vapor prezsure,P, [T, (p)] becomes a function of density. In out- Tine P—P,(p) =pR (T—T.(p)] + o1pRT,)Fp.D). oy ‘The function F(p,7) consists of two temperature-dependent functions esch with an isochoric (density dependent) coef- ficient. Letx(7)=7/T.,.u(p.T) "7 /T~(p). then, FaT)=Bp pT) + CVE. (6a) eT=In{ Cl +H)/2), (66) Wp =C/s)Inl1 + eu— 1 1/e (6) Bip) =By0 exp ~ 70), (6a) and CIR LE + Owe + GU" KU — voI_APK — HU). (6) Function (p,7) has an inflection versus u(7) at coexis- tence (zero curvature). Function Y(p,7) has large curva ture versus 4(7) approsching socnitence, but ite soufi cient, C(p), changes sign at a reduced density, 9 = 0.825. ‘The coeficients Bip), Cp) were tediously formulated by trial iting of the PpT data. To obtaina well-behaved critical isotherm, we constrain the slope ofthe critical isochore to ‘equal the slope of vapor-pressure Eq (1), both at the critical point, via the least-squares program of McCarty." Parameters and cooffcients for Eq. (6) are 72082, 5m33, €=70, o9=0825 B= 327166657, C= 2438401246, C,= — 20376962 79, C= —75.609 064 80. ‘Deviations of experimental densities and pressures from the EOS, Eq, (6), are presented in Table 9. At the bottom of each author's individual table im Lable ¥, Op/p av. 18 the ‘rend of density deviations, obtained asthe average of signed ‘relative deviations in percent. |AP/P | av. is the average of ReLwt* wep 1D Author/war © rk pmo Pts NPY me mene ‘57 Ramsay, 187 (Ret 53) ol oor 0 +R 53 Amapat 1853, (Re. 2) a0 asene jon OT “068 as 13 Bekgman, 1913 (Rel 9) 00 rsa8 won 8 lio Bt 38 Lashakow, 1939 (Ret 39) 00. 0337 1097 7 38 e2t 13 ‘36 Kretschme, 194 (Ret 35) 00 ‘006-0037 oro Skea 55 ety, 1955 (Rel 50) 00 om2-029 07 a4 a6 ohare, 1967 (Ref 71) OT ime 4 Lor os & Kodehdker, 1970 (Ret 38) 0238-473 omm-16 12743 Gs 70. Finkelsen, 1970(Ref. 19) 473.573 e1ang 13 Tor 6s Machado, 983 (Ret 42) 123294489 158256 02 for 33 98 Seaty, 1985 (Re. 63) sl es 2m 330 moO? “ada @ Viral Eg, 1985 a1 800 ona sae 1 07 028 Rel wi ses BA |4.Phys. Chem. Ret. Data, VoL. 16, No 4, 1087,ana ROBERT D. GOODWIN Table 8 Compara of 1D ale (92) Zubrey Far aa ‘i vloselelsted fom fo OD ‘Ag = os24620sel02 13 Sohatiossaioe al (ata) (ee) om. Yo Ohne Cisater O.9st00 0.38 1998 sims O°3anen “0.18 Xap 9.300 Gcaoses yeaa? 8.38 Top ovaena Scion ona 0.31 Tea paras were aa 45 oasieetat At iseonsceoe ee Too omit 3.87 0,s08eo 0.90851 0.07 Too 0.1168 £1049. 696699 ol9e689 8.02 Kao oes S082 GSH Qa cO8h Vion 0°49 31107 Olabia Oley 0.08 100 5's683 18.999 G.4rere octane8 “0.01 Ta pane, ee Seat UN itotherm ST = 453150 K i: aga ISS, sev ter (iva) (ee) HS OERy CRIES foe $8 1:00 0:8075 23.079 0.75860 9.76086 -0.31 ERAGE ETE SOs SMe os Tile 8 Comparten of HD ease (3) Zotar 1 eta ‘wih values nets fm Eg = Conte Ap > Gusmsitcot 3 obmsmaceo: ALT “taagonooo wee mvt tr (ei) ale) TR OMS S557 Gwon Osos 0.33 1.00 Olaois 13/369 Ocaumop OceEs00 0:00, 1.00 016387 1395 Olastas Ovasast Hop 099% slana olbrass 0.61389 Kon olsen bi2ep olinae lms ito 11306151381 olohwes ocane8s 4.00 1912682 200590 0°2646) 026463, Tas pane ong devon OOP intern 5 T= ais K ‘Are -eaarisiatio, 22 2 aissanseot 1S 5 cSessteat a = aioe) ‘Ag = asmispsicto0) a Too 018429395 G:9asnt Ols6ee?-0.08, 1.00 012939 st"384 S'paset ocsase7 “0.08 100 01730 35.688 esse Xo Olan tao 253386 cto Nop 1814352218000, iF daa pone Senge Govan OT enn i aes ecm aS 2 aint rr tee) tale) Dow Hoe Oc3ea8 4/908. Gcaaary ovgsiay 0.06 Hoo o:7177 262002 Ocaeiea ovesaa? 0.25 100 150935 Secns2 Olanss9 ocenaye 9:05 100 1 S048 fe.one 0.23210 0.33225 0.02 To 2.793 63.200 O'sui3e O'Stiea “o-as Hop ona? 4880 Stee olsisia “0.19 Hop HGo 42.960 oiier lids 0.31 Hoo 16°73 140/390 ocaeors O:a0194 9.39 Hoo 17-7121 202°599 oc28016 O:a%e90 0.09 tia pane serge deinen OFT‘THERMODYNAMIC PROPERTIES OF METHANE 813 Tobe 8 Conroe of 1 eo (9) Zt A te Tile 8 Comprar of et (2 tr fo Soar cael ome a - Sra ad om GS ec aaa ium 17 Sasw inom Tas 27 agate fu jap Prercoeeics Aor adaneseaon mF ADS cieotar mn Ga) ed om $5 Shorten I dds Tse oem oom 0.00 7 rao Kio [ise anes oles octet 2.00 Tap teeny esben O28 Oc3nae6 “0.00 ie Ba 1-aoTe io a. 4 ae paions evemegs vinta oR 1.00 80.400 0.46918 0.47027 — Sse io isin mess 0.9 ers eet 9 680 Onis eau aearrenen iw fa50 6.30 peau 100 a 0.2909 le eae 100 15130 0.26878 0.268 ee is Hisie Sis S388 eniematent 1.00 89.350 0.21998 0.22000 éi.__twr_(#ia)_(a)_Dv. Bei iter] ver reek eneses cee Tao 1 aan oni ote 0.08 100 apie 51a o.ansie 0.2080 NS ila Gow ogi cane ost to lechaer desii0_ 0.390% door He itn ith ose oSes 20 1S EBM HRo eit sree 0s 3a pi weg avin CHO Fe 158) RS oi on or Hao ScSe indir ots oltsi a.0r at ae rents SH See Sa : eet rah Goede Getta “0 cena LB pu Sintss 9.08 = 7a Noo tnsses 8.16938. -0.09 ea nnd Ds im ee cide “es ® Bsn 9.9870 6.05 tees oe a ie Sime piscine. Lio toss Sans 3.8, 18 SS SSSI 83 Fda iow temps Son ie Sno ote Sos he Scie Olsen 80s ee io Same olaie 03 Eameawen i Sims elaaee Sloe AL Domenie 100 03846 013889 oe pepearey $00 7.3070 94.330 0.29903 0.29967 0.35 Nie acim Sedan laste ovssnet co.o8 oie eT ae Kio Soom Sesie ase oaass oles eae a He ise isu ove eae ote 1.00 e209 2a o.snrr o.aoms 0.03 1 LER WEE does 8.360 8.2 Kin Se Bite ote es 28 1 tes Uns ocanem oases “0.08 ¥l00. 1419573 86.030 0.16830 0.16861 -0-18, 1.00, 210.020 0.29581 0.29477 0.25. MBSE ie OA) Sata 2:8 21 dw pin, seg eit 010% |. Phys. Chem Re. Data, Vo. 16, No.4, 1887ana ROBERT D. GOODWIN ‘Te 8 Comparian of ID le (93) uta Fe se sri vais ala Com ta) inom Te Fs Swe R ‘Aa = t33Mgoos001 100 15998 19 cs 0.ama03 0.40185 0.08 oo 2/3607 90.720 O\gn579 O.eres? -0°09 Ho 4st #3050 orsnea? Biseery 0.02 Foo 311929 3'te0 o:stane Osstea! “0.08 Hoo Mor ‘2:48 GcSndy Bisnis Ola. Hoo 4205 Sh460. Olanaos b:48zI9 0.08 Ho ie So SMG SLE ola) 00 $9502 uma.t30 Grazeee Oosates 0.48 Hoo 63626 103300 Oc3sney Blasiiy Dar 1.0) S248 tealeeo Glare Oianst “o.0F Top Whee 1041740 O°318e2 Ocaisal O16 19 S886) ThCoe0 OCBeN aeHed 606 100 13.0402 148.400 Blase? canes 2.0 ‘Az = 12091639601 ‘ke = Gazgraonacoan ivr ats) aie) _ Dew Noo "tes 44cear pistes pssease 0.17 Hop 2's643 $3.49 O.4enso O.4e201 0.08 Hoa 33990 S6-030 O:ss368 bcss¥ar | Ocor Yo dctats reesap Blabies Blssoay 8.08 Hop SUksio 10's Gvauasi Boaesee 0°15 100 Sceea0 110saGe Blaaste Bodlees 2:08 Hoo 6'S916 116/460 D'3eise D:38189 “0.09 100 9"30n) 120-t=D O:aeeet Os3eup 0.01 Hon TH 12ato 8.380 oe “ole: 190 $1396 138-330 B3Ts6 B.iga) “tsa 09 9/30se 130.330 O.30T17 o'soage 0.11 Noo 10/3601 136/130 6.39006 B:35099 | OcOe 100 109600 140.540 b.aname p.aseie -0.07 foo iPdond ig3:8t@ Ocdnner Snes 2.09 100 1416836 210°300 0.31766 0.31763. 0.01 8 Se pans avenge Gan OF ‘4. Phys. Chem. Ret. Data, Vo. 16, No.4, ‘Tle 8. Compe of 1D case (3) Zataey Hy t Sei alas eee fm 6 (| 5 2 awa a) {Urs 1065400 O° sete Sine lana ovessse T4809 1ls'Se0 O'Saasp O°deats 8.01 S:adso Layiain olioig osagots 0.00 bo 13s 148.010 B°atMKs 8caHeK8 “8:00 28283 Te pine, Bema Sev GR Iionarw 15 P= ss & mol tar Gru) fale) Dee 1001-97 61-680 0.80891 0.80534 -0.00 Hho Holes 22-36 Sins ocSioe aco, EG) 10°35 155-400 Stes ocdenee 0-08 100 12.3n3 200.030 G.3stos @.astos "0.00 Fa pine, avenge Svan OUT ‘Ar = “09507840400 win aw oom io aa irs Oeste 0.esie 0.08 Hoo 10s07 s00330 068944 O-e9001 0.08 40 39885 117.340 Glee Olentay “Oct 283 SHE UII St SS 8:8 Too 539% 180-610 Ova8a03 Ovak3ee 0.04 Yo 974904 140°%40 b.a80 Guages 0.00 Yop 314s 149"s80 DlaHor 0:43803 0:00 Top (3.3748 iao'sap Bvanaae Qvaaest “2.02 180 sOcH083 130-280 SSH PNT ORE 100 11-0810 206.280 9.38088 0:3b040 0.01 WT dam pn tre evn DO‘THERMODYNAMIC PROPERTIES OF METHANE 815 ‘Toble ae Comparoo of HD co (13) Hrdgeman Po dts with values caleuates ‘em (6) rn a le ple PGi P ahr else esis eave enters ears te ‘nor 205.150 35.7348 35.8805 0.56 W90.557 419.819 16.80 oot 2931180 2e.s260 2el2667 “0.90 G80e6s | AITO 17.16 D001 3935180 27.3524 295085 “b'92 1470998 129482 13.61 Bloor 393180 9778192 28-4466 “1116 1961-380 1703.62 15-12, bigot 293.180 a8.3n8a 28.7192 “1143 44S1.663 2094081 19.05 15001 2931180 26.7526 292376 “166 2961995 24819001858 1.001 303-180 24.3134 26.5394 70.85 980.665 548.856 15.87 8.001 3027180 27-0484 39/2923 “0190. 2470-998 901"588 19-02 0.001 309:180 27.6246 27/9463 “1.15 1961-390 1712.456 1483, dor 3oaz180 dectas6 26.5281 “1141 DASH 663 2106-686 16:38 oor M3180 35.3799 2s:3819 Lo"40 “490393 “44S.261 10-62 Bde Saltso 26.4042 26.3143 “0.80 9806ES R6N.3O 19.9 1001 3137180 26.8500 27.0828 “0°86 1470.99 1314-065 11:98 bioor Baliso d9.4sey 374487 “112 Yee a0 138.807 13a Bio SSS F985 FGM EGS HSHees 7asTea 18ST 0.001 313150 241453 2BlaTeR “Albt 2961995 514.560 17:00 Door 3231180 98.0389 2811338 “0.38 “4901383 ate.397 9138 (ol 323"150 25.8950 26.0912 0.76 980.655 69.817 12.78, 001 323150 29.9671 2715536 108 1961-380 146.333 12ST (01 3231150 27.786 28.1868 “Lia Steed 240.977 14.36 OI 323-150 26.2545 24.7022 “1156 941.995 25361391 15.99 OL 393150 24-7009 24° BNSt “Ors “UG0°339 “au9_716 "9°02 RAS dela7aa deleno “ol3k W90°998 Bale '9!60 BII180 2lo017 aTiaio“olse Heet-3a0 Teacaa7 18.9 HIS0 27-0246 27.9798 “1.38 Dusted 24651809 13.20, Bus"150 28.0878 da's2e3 “151 942 995. 2557"109 15.05 Maci50 2acsas aleie0 “ola “U0°339 “434 "5:89 B43.180 25-4601 25.6497 “0174 980.668 79.253 11.54 331180 26.2751 2614653 “0.73. 1470.998 M4T'S2S 916 3431150. 2619129 373907 “0/95 961.330 1978.793 10/87 Bd.180 3.9iad de.dsee Lute onn.dos Aston eas 353180 24.3607 belaase “olak “agol323. “aaav91s 10.46 353.180 2312915 28.4306 “ole 80.668 BNL-ISOH249 3531150 3610682. 26.3604 “0195 90.998 aguecen "9.2 3531150 2913898 Fei6isy“ilta dusileea aeolare 18 $53:180 27.7949 261867 11139 Do4L"995 2600.80 13.12, “Die pag, Gor mm - LDR avy ww = OR Pe oe ae a ah mm, i 4 Phys. Chem, Ret. Data, Vol. 1, Mo. 4 1887a6 ROBERT D. GOODWIN ‘Title 98 Campus of D cle (16) Sex Fi dea with vale clad on i ee Ee a EE Shoe hee eee to ee ee Sa Helo dive hom Sa Mat Soak cor fooe gue Rie 2 ee ee St ee Bae ee te eae ee Persie isu eee 29.1857 0.4 29.5812 er noe f pied a Ea SS BAS SS as Be made cael ca poy 23 ae i Siesmecamuies eae seed Seca fae ad sce re oe Be eas ie 3a ie $i ES BU Re Bees 9.001 252.350 27.3319 27.4628 10.600 cee on ls aes Sat ES Rare Beet oe sees Phi Chem, Rel Dat, Vo. 16 No.4 1067